In this study, the effect of type of lithium salts on the main properties of the nanostructure electrolytes was studied. Electrospinning process was applied to production of solvent-free PEO-based nanofibrous electrolytes containing various lithium salts, i.e., LiCl, LiClO4, and LiTFSI. Then, the characteristics of the electrospun nanofibers were evaluated by various techniques. The fraction of free ions was estimated by the FTIR spectrum. Also, to investigate the crystalline phases of the as-spun electrolytes, the samples were subjected to X-ray analysis. The highest room temperature ionic conductivity of the fabricated electrolytes was obtained as 0.33 mS cm(-1)by the addition of 1.5 wt% LiClO(4)into the nanofibers. Furthermore, the cycling stability of the as-spun structures was enhanced by increasing the amount of LiClO(4)and LiCl salts in the produced nanofibers. The results implied that the prepared nanofibers are good candidates as solvent-free electrolytes for Li-ion batteries.